JP5557692B2 - Negative electrode active material for non-aqueous secondary battery and non-aqueous secondary battery - Google Patents

Description

  The present invention relates to a negative electrode active material for a non-aqueous secondary battery and a non-aqueous secondary battery.

  As a non-aqueous secondary battery, a lithium-ion secondary battery using a non-aqueous electrolyte and using lithium ions for a charge / discharge reaction has been put into practical use. Lithium ion secondary batteries have a higher energy density than nickel metal hydride batteries and the like, and are used as secondary batteries for power sources of portable electronic devices. However, with the recent high performance and miniaturization of portable electronic devices, there is a demand for further increase in capacity and miniaturization of lithium ion secondary batteries as power sources. In order to realize this, it is essential to increase the capacity of the negative electrode active material used for the negative electrode.

Currently, a carbon-based material is used for the negative electrode active material, and lithium ions are occluded / released by intercalating / deintercalating lithium ions between graphene layers, and the theoretical capacity is 372 Ah / kg. . However, the actual capacity of carbon-based materials is close to the theoretical capacity, and a dramatic increase in capacity cannot be expected. Therefore, the search for alternative materials for carbon-based materials has been actively conducted, and high capacity can be expected by the alloying ^/ dealloying reaction as shown by the formula of xLi ⁺ + M + xe ⁻ ⇔LixM (M is a metal). There is a great interest in alloy negative electrodes (or metal negative electrodes) that perform charge and discharge reactions. For example, the theoretical capacity of silicon is 4200 Ah / kg, and the theoretical capacity of tin is 990 Ah / kg, which is several times to 10 times the theoretical capacity of carbon-based materials.

  However, it is known that this alloy negative electrode has a larger volume change due to charging / discharging than the carbon material, and expands to 420% for silicon and 360% for tin when lithium ions are inserted. The electrode structure cannot be maintained due to the stress caused by the volume change, and the cycle characteristics are poor as compared with the carbon-based material, and it is necessary to improve it.

  Therefore, Patent Document 1 and the like propose to maintain the structure and improve the cycle characteristics by alloying with a matrix component that does not react with lithium ions, but the cycle characteristics are poor and cannot be put to practical use.

  In Patent Document 2, a conductive layer formed by bonding conductive particles so that voids are generated around the conductive particles is provided on the current collector, and the active material is efficiently obtained by allowing the active material to exist in the voids. A method of dispersing has been proposed. In Patent Document 3, active material particles and a metal oxide layer are provided, the surface of the particles is coated with a metal material, and the volume change is mitigated by having voids between the coated particles, thereby suppressing structural collapse. A method has been proposed. However, in any of the methods, the volume expansion of the negative electrode active material primary particles themselves cannot be suppressed, and the powder may be pulverized by charge / discharge to deteriorate the cycle characteristics.

  Furthermore, Patent Document 4 proposes a method for preventing deterioration of the adhesion between the current collector and the active material layer by providing a conductive material having pores between the active material layer and the current collector. The volume expansion of the electrode cannot be suppressed, and the electrode structure may not be maintained.

JP 2009-32644 A JP 2007-194024 A JP 2009-277509 A JP 2008-77993 A

  The problem to be solved by the present invention is caused by the stress generated by the volume change in the negative electrode active material for non-aqueous secondary battery and the non-aqueous secondary battery by suppressing the volume change of the negative electrode active material primary particles themselves. The primary particle of the negative electrode active material to be prevented from spreading cracks, and the conductive network is maintained even if a part of the negative electrode active material primary particle structure collapses due to the volume change, thereby improving the cycle characteristics. That is the point.

  The negative electrode for a non-aqueous secondary battery according to the present invention includes an inner core portion in a primary particle, wherein the negative electrode active material is composed of either silicon or tin and at least one element selected from elements that do not react with lithium. And the outer peripheral portion has holes, and a conductive material is introduced into the holes. As shown in FIG. 1, each of the inner core portion and the outer peripheral portion is composed of either silicon or tin and at least one element selected from elements that do not react with lithium, and the element that does not react with lithium maintains the structure. It functions as a component that bears and prevents structural collapse. In addition, by having vacancies in both the inner core portion and the outer peripheral portion inside the primary particles, the vacancies absorb the volume change due to the charge / discharge reaction, and the entire primary particles can be relaxed. The holes prevent crack extension and prevent structural collapse. Furthermore, by introducing a conductive material inside the pores, even if a part of the structure collapses, the conductive material can maintain the conductive network by connecting the parts separated by the collapse. And increase in resistance can be suppressed. These improve the cycle characteristics.

  Further, the present invention is characterized in that the conductive material is a transition metal. Since the conductive material is a transition metal, it is preferable because it has good electric properties.

  Further, the present invention is characterized in that the conductive material is any one of copper, nickel, and silver. It is more preferable that the conductive material is copper, nickel, or silver because it has better electric conductivity.

  Further, the present invention is characterized in that the conductive material is introduced by a plating method. By using a plating method, a conductive material can be introduced into the pores. In addition, alloying due to thermal diffusion between the conductive material and the surface of the primary particles can be suppressed, and deterioration of conductivity can be prevented, which is preferable.

  Further, the present invention is characterized in that the conductive material is introduced by 20% by weight or more. By introducing 20% by weight or more of the conductive material, the DC resistance value of the negative electrode can be prevented from increasing even after charge / discharge. On the other hand, if it exceeds 50% by weight, the amount of the active material is relatively reduced, and the capacity is lowered.

  Further, the present invention is characterized in that the degree of dispersion, which is a value obtained by dividing the standard deviation of the distance between the centers of gravity of the holes by the average of the distance between the centers of gravity of the holes, is 1 or less. Since voids that prevent crack extension are uniformly arranged in the negative electrode active material, structural collapse can be suppressed. Moreover, uneven distribution of stress can be avoided by the uniform distribution of holes.

  In addition, the present invention is characterized in that an average particle diameter of the primary particles of the negative electrode active material is 50 μm or less. By setting the average particle diameter to 50 μm or less, the absolute amount of volume change can be suppressed. Moreover, when it is 1 micrometer or more, since a non-surface area does not become excessive too much and reaction with electrolyte solution can be suppressed, it is preferable.

  Further, the present invention is characterized in that an average pore diameter of the pores is 1 μm or less. By setting the average pore diameter to 1 μm or less, it is possible to increase the number of pores that prevent crack extension. On the other hand, when the thickness is 0.1 μm or more, it is difficult to introduce the conductive material, which is not preferable.

  Further, the present invention is characterized in that the porosity of the holes is 5% or more. If the porosity is less than 5%, the volume change cannot be suppressed. Moreover, when it exceeds 80%, it becomes more than a volume change, an effect does not change, and a capacity | capacitance falls conversely.

  In addition, the present invention is characterized in that the average crystallite diameter of silicon and tin of the negative electrode active material is 5 μm or less. By setting the crystallite diameter to be equal to the pore diameter, it is preferable that the expansion of the crystallite can be absorbed by the pores and the volume expansion can be further suppressed.

  Further, the present invention is characterized in that the average distance between pores of the negative electrode active material is 3 μm or less. It is preferable that the average distance between pores is 3 μm or less because crack extension can be prevented. Further, when the thickness is 0.01 μm or less, the portion composed of either silicon or tin and at least one element selected from elements that do not react with lithium becomes too thin compared to the vacancies, and the negative electrode active material primary particles This is not preferable because the strength of the resin is lowered.

  Further, the present invention is characterized in that 10% by weight or more of silicon or tin contained in the negative electrode active material is contained. When the content of silicon or tin is less than 10% by weight, the capacity is lowered, which is not preferable. Moreover, when it becomes 95 weight% or more, the component which contributes to a structure maintenance will fall.

  Further, the present invention is characterized in that the element that does not react with lithium is any one of vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, gold, indium, titanium, and zirconium. . By using vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, gold, indium, titanium, or zirconium, the negative electrode active material is preferable because it has good conductivity.

  In addition, the present invention is prepared by preparing particles having vacancies in both the inner core portion and the outer peripheral portion inside the primary particles by a molten metal quenching method and introducing a conductive material into the vacancies of the primary particles. It is characterized by that. Holes are formed by manufacturing using a molten metal quenching method. In addition, the crystallite diameter is preferably reduced.

  Further, the present invention is characterized in that particles having pores in both the inner core portion and the outer peripheral portion inside the primary particles are produced by a single roll method. By using a single roll method, it is possible to carry out ultra-rapid cooling, which is preferable because the crystallite diameter and pore diameter are reduced.

  In addition, the present invention is characterized in that the negative electrode manufactured using the negative electrode active material has an increase rate of the DC resistance value after 10 cycles of 20% or less with respect to the DC resistance value in the initial state. Longer life is achieved by setting the rate of increase in DC resistance to 20% or less.

  The non-aqueous secondary battery of the present invention is characterized by using the above-described negative electrode active material for non-aqueous secondary batteries. By using the negative electrode active material for a non-aqueous secondary battery of the present invention, a secondary battery having a high capacity and a long life can be provided.

  Since the negative electrode for a non-aqueous secondary battery of the present invention has pores in the primary particles of the negative electrode active material, even if the volume of silicon or tin changes greatly due to charge / discharge, the volume change can be absorbed by the pores, And since it has a void | hole in both an inner core part and an outer peripheral part, it can avoid that a volume change localizes and can suppress structural collapse. In addition, the structural collapse can be suppressed by the pores preventing crack extension. Furthermore, the introduction of a conductive material inside the pores allows the conductive network to be maintained even if a part of the structure collapses, thereby preventing an increase in resistance and improving cycle characteristics. can get.

It is a conceptual diagram of the negative electrode active material of this invention. It is a cross-sectional scanning electron micrograph of Example 1 of the present invention. It is a cross-sectional scanning electron micrograph of Example 2 of the present invention. It is a cross-sectional scanning electron micrograph of the comparative example 1 of this invention. It is a mapping figure of the nickel element of the cross section of Example 1 of this invention. It is a mapping figure of the nickel element of the cross section of Example 2 of this invention. It is a mapping figure of the nickel element of the cross section of the comparative example 1 of this invention. It is a schematic diagram of the non-aqueous secondary battery of this invention.

  Hereinafter, embodiments of the present invention will be described in detail.

(Negative electrode active material)
The negative electrode active material is composed of either silicon or tin and at least one element selected from elements that do not react with lithium. It may contain both silicon and tin. It does not matter as long as it contains silicon or tin, but it is preferable that silicon is contained in an amount of 10% by weight or more, and tin is contained in an amount of 50% by weight or more because a high capacity can be obtained. When both silicon and tin are included, the total weight of silicon and tin is preferably 10% by weight or more. On the other hand, if it is 95% by weight or more, the component contributing to the structure maintenance is undesirably lowered. Furthermore, it is preferable to use tin having a high diffusion rate of lithium ions and high conductivity.

  As an element that does not react with lithium, an element that does not react with lithium at all can be used, as long as it is an element that is less reactive with lithium than silicon and tin. The element that does not react with lithium is preferably good-electricity, and is preferably a transition metal element. Examples include vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, gold, indium, titanium, and zirconium. In particular, iron, nickel, copper, cobalt, manganese, silver, and gold are preferable because of their high conductivity.

  The average particle diameter of the negative electrode active material primary particles is preferably 50 μm or less. If it is larger than 50 μm, the absolute amount of volume change due to charge / discharge increases, which is not preferable. Moreover, when it is 1 micrometer or more, since a non-surface area does not become excessive too much and reaction with electrolyte solution can be suppressed, it is preferable. Here, the primary particle is a continuous solid, for example, a polycrystalline body bonded by a metal bond, and a powder particle simply aggregated by van der Waals force is defined as a secondary particle. The average particle diameter is a median diameter D50 value measured by a laser diffraction type particle size distribution measuring instrument in a state where aggregation is solved by applying ultrasonic waves.

  The crystallite diameter of silicon and tin is preferably 5 μm or less. When the thickness is 5 μm or less, it is preferable because localization of stress caused by a volume change during charge / discharge can be avoided. Further, the thickness is more preferably 1 μm or less because the stress can be made uniform and the maximum stress can be suppressed. The crystallite diameter is observed with a scanning electron microscope or a transmission electron microscope, and the average crystallite diameter is measured. An electron micrograph of the sample is taken, the particle diameter of the crystallites observed in an arbitrary area in the photograph is measured, and the average value is obtained as the crystallite diameter. It is desirable to obtain an average value so that the number of measurement crystallites is at least 20 or more. When the cross section is not circular, the average value of the maximum length and the minimum length is regarded as the particle diameter of the crystallite.

  Both the inner core portion and the outer peripheral portion inside the primary particles of the negative electrode active material have pores. The shape of the hole is not particularly limited, and examples thereof include a spherical shape, a cylindrical shape, a conical shape, a cubic shape, and a rectangular shape. The inner core portion is the inside of a sphere having a diameter that is 50% of the particle diameter of the primary particles centered on the center of gravity of the primary particles, and the outer peripheral portion is the outside thereof. By having pores in both the inner core portion and the outer peripheral portion inside the primary particles, the volume change of the negative electrode active material can be suppressed uniformly. Moreover, it is preferable that the degree of dispersion, which is a value obtained by dividing the standard deviation of the distance between the center of gravity of the holes by the average of the distance between the center of gravity of the holes, is 1 or less. Since the pores are uniformly dispersed inside the primary particles, crack extension can be suppressed. The average value of the distance between the centroids of the holes and the standard deviation of the distance between the centroids of the holes can be obtained, for example, by taking an electron micrograph of the cross section of the negative electrode active material and analyzing the image.

  When the average value of the pore diameter is 1 μm or less, the number of pores increases and the pores can exist in the particles without unevenness. Moreover, the number of vacancies preventing crack extension is increased, and structural collapse can be suppressed, which is preferable. When the thickness is 0.5 μm or less, the number of vacancies is further increased, and the unevenness of the vacancies is further eliminated. Further, the number of vacancies preventing crack extension is further increased, and the cycle characteristics are improved. On the other hand, when the thickness is 0.1 μm or more, it is difficult to introduce the conductive material, which is not preferable. The average value of the pore diameter is a value of an average equivalent circle diameter obtained by taking an electron micrograph of a cross section of the negative electrode active material and obtaining an image analysis.

  The average inter-hole distance is preferably 3 μm or less because crack extension can be further prevented and structural collapse can be suppressed. Further, when the thickness is 0.01 μm or less, the portion composed of either silicon or tin and at least one element selected from elements that do not react with lithium becomes too thin compared to the vacancies, and the negative electrode active material primary particles This is not preferable because the strength of the resin is lowered. The average distance between holes is a value obtained by subtracting the average hole diameter from the average distance between the centers of gravity of the holes.

  The porosity is preferably 5% or more. The volume change accompanying charging / discharging can be relieved by setting the porosity to 5% or more. Moreover, when it exceeds 80%, it becomes more than a volume change, an effect does not change, and a capacity | capacitance falls conversely. The porosity is the ratio of the area occupied by the vacancies in the photograph obtained by taking an electron micrograph of the negative electrode active material.

  A conductive material is introduced into the pores inside the primary particles of the negative electrode active material. By introducing a conductive material into the vacancies inside the primary particles, a conductive network can be maintained even if a part of the active material structure collapses due to volume expansion. The introduction may be in any form as long as a conductive material exists inside the pores. Further, a conductive material may be introduced into all the holes, or a conductive material may be introduced into a part of the holes. Needless to say, the pore surface may be covered with a conductive material. The conductive material may be coated on the particle surface. The coating may cover the entire surface or may cover a part.

  The conductive material preferably has higher conductivity than the alloy used for the primary particles of the negative electrode active material. A more conductive network can be maintained. As the conductive material, a transition metal having good conductivity is preferable. Copper, nickel, and silver are more preferable because they have good conductivity.

  The conductive material is preferably introduced in an amount of 20% by weight or more of the negative electrode active material. It is preferable that 20% by weight or more of the conductive material is introduced because an increase in resistance of the negative electrode due to charge / discharge can be suppressed. More preferably, 30% by weight or more of the conductive material is introduced. It is more preferable that the conductive material is introduced in an amount of 30% by weight or more because the resistance increase of the negative electrode due to charge / discharge can be further suppressed. Furthermore, if it exceeds 50% by weight, the amount of the active material is relatively small, which is not preferable because the capacity is lowered.

  As a method for producing primary particles, a molten metal quenching method can be used. The crystallite diameter can be made finer by using the molten metal quenching method. For example, single roll method, twin roll method, centrifuge method (vertical type), centrifuge method (horizontal type), single roll method with planetary roll, gun method, piston anvil method, torsion catapult method, in water flow There are spinning method, spinning in spinning solution, glass-coated spinning method, gas atomizing method, and water atomizing method. In addition, it is more preferable to use a single roll method with a rapid quenching rate, which makes the crystallite size finer, and the quenching rate differs between the surface that contacts the cooling substrate and the surface that does not contact, and a temperature gradient occurs during cooling. It is also preferable from the viewpoint of forming.

  As a method for introducing the conductive material into the primary particles, a plating method can be used. By using a plating method, a conductive material can be introduced into the pores. In addition, since excessive heating is not required, alloying between the conductive material and the primary particle surface can be prevented, and a decrease in conductivity due to alloying of the conductive material can be prevented. Either an electrolytic plating method or an electroless plating method can be used, but the electroless plating method is preferable because a conductive material can be easily introduced into the powder.

(Negative electrode)
By using the negative electrode active material for a non-aqueous secondary battery of the present invention, a long-life negative electrode for a non-aqueous secondary battery can be produced. The negative electrode preferably has an increase rate of the DC resistance value after 10 cycles of 20% or less with respect to the DC resistance value in the initial state. The cycle characteristics are improved by setting the rate of increase in the DC resistance value to 20% or less.

(Secondary battery)
By using the negative electrode for a non-aqueous secondary battery of the present invention, a long-life non-aqueous secondary battery can be produced.

  Hereinafter, embodiments according to the present invention will be described in detail. However, the present invention is not necessarily limited by these examples.

〔Example〕
Example 1
80 parts by weight of tin and 20 parts by weight of cobalt were mixed, melted by an arc melting method in an argon atmosphere, and cooled to obtain an alloy.

  The obtained alloy was pulverized to a size of 5 mm to 10 mm square, melted by a high-frequency heating method in an argon atmosphere, and quenched by a single roll method to obtain a ribbon-like quenched alloy. The ribbon-like quenched alloy was pulverized with a mortar and classified by passing through a sieve having an opening of 45 μm to obtain primary particles.

  The average crystallite size of the primary particle cross section was measured by scanning electron micrograph and found to be 0.5 μm. Further, a scanning electron micrograph of the cross section of the primary particle was analyzed by image analysis software (A image-kun, manufactured by Asahi Kasei Engineering Co., Ltd.), and the porosity, average pore diameter, degree of dispersion, and average center-to-center distance were determined. As a result, the porosity was 23.7%, the average pore diameter (equivalent circle diameter) was 0.38 μm, the degree of dispersion was 0.42, and the average distance between the centers of gravity was 2.9 μm.

  The obtained primary particles were added to a nickel plating solution heated to 60 ° C. (Top Chemialloy 66, manufactured by Okuno Pharmaceutical Co., Ltd.) and stirred for 30 minutes to obtain a negative electrode active material. Table 1 shows the results of elemental analysis of the obtained negative electrode active material by high frequency inductively coupled plasma optical emission spectrometry (ICP-AES).

(Example 2)
It was prepared in the same manner as in Example 1 except that the stirring time was 60 minutes. Table 1 shows the results of elemental analysis of the obtained negative electrode active material by high frequency inductively coupled plasma optical emission spectrometry (ICP-AES).

(Comparative Example 1)
It was produced by the same method as in Example 1 except that nickel plating was not performed.

(Tissue observation)
The cross sections of the negative electrode active materials of Examples 1 and 2 and Comparative Example 1 were observed with a scanning electron microscope. The results are shown in FIGS. In addition, nickel element mapping was performed by energy dispersive X-ray analysis. The results are shown in FIGS.

  As shown in FIGS. 2 to 4, it can be seen that the negative electrode active materials of Examples 1 and 2 and Comparative Example 1 have voids in both the inner core portion and the outer peripheral portion inside the primary particles. 5 and 6, it can be seen that nickel (conductive material) is introduced into the pores of the negative electrode active materials of Examples 1 and 2 and the primary particle surfaces. On the other hand, as shown in FIG. 7, it can be seen that the negative electrode active material of Comparative Example 1 has no conductive material introduced therein.

(Electrode property evaluation method)
The negative electrode active materials of Examples 1 and 2 and Comparative Example 1 were each kneaded with acetylene black as a conductive agent and a solution of polyvinylidene fluoride dissolved in N-methylpyrrolidone as a binder to prepare slurry. The obtained slurry was uniformly coated on the copper foil using a coating machine. Pressurized after drying in air. Then, it was dried in vacuum. As the electrolytic solution, a solution obtained by adding 1M LiPF ₆ to a solvent obtained by adding vinylene carbonate to a mixed solvent of ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate was used. Lithium metal was used for the counter electrode.

The charge and discharge test, a constant-current constant-voltage charge until the 0.01V (vs.Li/Li ^+), discharge was constant current discharge until the 2V (vs.Li/Li ^+). Table 2 shows the initial coulomb efficiency and capacity retention rate.

  In addition, the DC resistance value after 5 seconds of current application in the initial state and the state of charge (SOC) 50% after 10 cycles and 0.1 CA was measured, and the DC resistance value after 10 cycles increased relative to the DC resistance value in the initial state. The rate was determined and the results are shown in Table 2. If the DC resistance value after 10 cycles is less than the initial DC resistance value, the DC resistance value increase rate is regarded as 0%.

  As shown in Table 2, the negative electrode active materials of Examples 1 and 2 have higher coulomb efficiency and capacity retention than the negative electrode active material of Comparative Example 1. That is, by introducing a conductive material into the primary particles, the initial Coulomb efficiency and cycle characteristics were improved, and it was shown that the negative electrode active material for a non-aqueous secondary battery of the present invention has a long life.

  In addition, as shown in Table 2, the negative electrode produced using the negative electrode active materials of Examples 1 and 2 has a significantly reduced direct current resistance increase rate as compared with the negative electrode produced using the negative electrode active material of Comparative Example 1. I understand that. That is, it was shown that a conductive network is maintained even after charge and discharge by creating a negative electrode using the negative electrode active material of the present invention in which a conductive material is introduced into primary particles.

  The negative electrode active material for a non-aqueous secondary battery obtained in the present invention can be expected to be applied to a mobile body that requires a large-sized lithium ion secondary battery having excellent capacity and a power source for stationary power storage.

DESCRIPTION OF SYMBOLS 1 Negative electrode active material 2 Conductive agent 3 Binder 4 Current collector 5 Hole 6 Conductive material 7 Inner core part 8 Outer part 9 Inner core hole 10 Outer part hole 11 Positive electrode plate 12 Negative electrode plate 13 Separator 14 Positive electrode Lead 15 Negative electrode lead 16 Battery can 17 Packing 18 Insulating plate 19 Sealing lid

Claims (17)

  Consisting of either silicon or tin and at least one element selected from elements that do not react with lithium, and having vacancies in both the inner core and outer periphery of the primary particles, and A negative electrode active material for a non-aqueous secondary battery, characterized in that the inner surfaces of the pores are covered with a conductive material layer (excluding those in which a conductive material is introduced into all the pores).   The negative electrode active material for a non-aqueous secondary battery according to claim 1, wherein the conductive material is a transition metal. The negative electrode active material for a non-aqueous secondary battery according to claim 1 or 2 , wherein the conductive material is any one of copper, nickel, and silver. The negative electrode active material for nonaqueous secondary batteries according to any one of claims 1 to 3 , wherein the conductive material is introduced by a plating method. The negative electrode active material for a nonaqueous secondary battery according to any one of claims 1 to 4 , wherein the conductive material is introduced in an amount of 20% by weight or more. In the active material for a non-aqueous secondary battery according to any one of claims 1 to 5 , a dispersity which is a value obtained by dividing an average deviation of the distance between the center of gravity of the hole by an average of the distance between the center of gravity of the hole. A negative electrode active material for a non-aqueous secondary battery, wherein the negative electrode active material is 1 or less. The negative electrode active material for a nonaqueous secondary battery according to any one of claims 1 to 6 , wherein the primary particles have an average particle size of 50 µm or less. The negative electrode active material for a non-aqueous secondary battery according to any one of claims 1 to 7 , wherein an average pore diameter of the pores is 1 µm or less. The negative electrode active material for a non-aqueous secondary battery according to any one of claims 1 to 8 , wherein the porosity of the pores is 5% or more. The negative electrode active material for a non-aqueous secondary battery according to any one of claims 1 to 9 , wherein the silicon or tin has an average crystallite diameter of 5 µm or less. 11. The negative electrode active material for a non-aqueous secondary battery according to claim 1 , wherein an average inter-hole distance between the holes is 3 μm or less. The negative electrode active material for a non-aqueous secondary battery according to any one of claims 1 to 11 , wherein silicon or tin is contained in an amount of 10% by weight or more. The negative electrode active material for a non-aqueous secondary battery according to any one of claims 1 to 12 , wherein the element that does not react with lithium is vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, gold, or indium. A negative electrode active material for a non-aqueous secondary battery, wherein the negative electrode active material is at least one element selected from titanium, zirconium and zirconium. The negative electrode active material for a non-aqueous secondary battery according to any one of claims 1 to 13 , wherein particles having pores in both the inner core portion and the outer peripheral portion inside the primary particles are prepared by a molten metal quenching method, A negative electrode material for a non-aqueous secondary battery, which is produced by introducing a conductive material into the pores of particles. The negative electrode active material for a non-aqueous secondary battery according to any one of claims 1 to 14 , wherein particles having pores in both the inner core portion and the outer peripheral portion inside the primary particles are produced by a single roll method. A negative electrode active material for a non-aqueous secondary battery. The active material for a non-aqueous secondary battery according to any one of claims 1 to 15 , wherein an increase rate of a DC resistance value after 10 cycles of a negative electrode produced using the active material is higher than a DC resistance value in an initial state. A negative electrode active material for a non-aqueous secondary battery, characterized by being 20% or less. A nonaqueous secondary battery comprising: a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the negative electrode active material for a nonaqueous secondary battery according to claim 1 is used as the negative electrode active material of the negative electrode. .

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